Lower groundwater ¹⁴C age by atmospheric CO₂ uptake during sampling and analysis

Uptake of atmospheric CO₂ during sample collection and analysis, and consequent lowering of estimated ages, has rarely been considered in radiocarbon dating of groundwater. Using field and laboratory experiments, we show that atmospheric CO₂ can be easily and rapidly absorbed in hyperalkaline solutions used for the extraction of dissolved inorganic carbon, resulting in elevated ¹⁴C measurements. Kinetic isotope fractionation during atmospheric CO₂ uptake may also result in decrease of δ¹³C, leading to insufficient corrections for addition of dead carbon by geochemical processes. Consequently, measured ¹⁴C values of groundwater should not be used for age estimation without corresponding δ¹³C values, and historical ¹⁴C data in the range of 1 to 10% modern Carbon should be re-evaluated to ensure that samples with atmospheric contamination are recognized appropriately. We recommend that samples for ¹⁴C analysis should be collected and processed in the field and the laboratory without exposure to the atmosphere. These precautions are considered necessary even if ¹⁴C measurements are made with an accelerator mass spectrometer.